Mesut Ozil scored his first goal for Arsenal and set up another for Olivier Giroud as Rafa Benitez's return to England was ruined by anothr sublime display by Arsene Wenger's in-form side.
Ozil opened the scoring after just eight minutes, bursting into the penalty area to latch on to Aaron Ramsey's low cross and steering a quite brilliant left-footed finish past Pepe Reina - on loan from Liverpool - in Napoli's goal.
Giroud doubled the lead just seven minutes later to leave the game all but over after just quarter of an hour. The French striker scored his sixth goal of the season from close range after Ozil burst down the right channel and squared for his Gunners team-mate to tap in.
Benitez, a familiar foe at the Emirates Stadium following his spells as Liverpool and Chelsea boss in the past, was powerless to stop the home side as Arsenal dominated throughout and rarely offered Napoli a sniff at goal.
The Gunners coasted to a second successive victory in what appeared to be a 'group of death' when the draw was made and Wenger's men sit top of the Group F with a maximum six points ahead of their double header against Borussia Dortmund, last year's finalists.
Too hot to handle: Mesut Ozil (centre) celebrates the opening goal with his Arsenal team-mates
Match facts
ARSENAL: Szczesny, Sagna, Mertesacker, Koscielny, Gibbs, Arteta, Flamini, Ramsey (Monreal 88), Rosicky (Wilshere 63), Giroud, Ozil.
Subs not used: Fabianski, Vermaelen, Bendtner, Jenkinson, Gnabry.
Goals: Ozil 8, Giroud 15
NAPOLI: Reina, Mesto, Albiol (Fernandez 83), Britos, Zuniga, Behrami, Inler, Callejon (Zapata 77), Hamsik, Insigne, Pandev (Mertens 61).
Subs not used: Rafael Cabral, Dzemaili, Armero, Cannavaro.
Referee: Milorad Mazic (Serbia)
Subs not used: Fabianski, Vermaelen, Bendtner, Jenkinson, Gnabry.
Goals: Ozil 8, Giroud 15
NAPOLI: Reina, Mesto, Albiol (Fernandez 83), Britos, Zuniga, Behrami, Inler, Callejon (Zapata 77), Hamsik, Insigne, Pandev (Mertens 61).
Subs not used: Rafael Cabral, Dzemaili, Armero, Cannavaro.
Referee: Milorad Mazic (Serbia)
What a finish: Ozil latched on to Aaron Ramsey's cross to side-foot the ball past Pepe Reina
Back of the net: The German playmaker's cool finish flies past the helpless former Liverpool goalkeeper
Back of the net: The German playmaker's cool finish flies past the helpless former Liverpool goalkeeper
Tap-in: Oliver Giroud (centre) converts Ozil's cross at the near post to score the second easily past Reina
Flying start: The French striker celebrates his sixth goal of a successful season so far
All the time in the world: Ozil takes a touch during a stellar performance for his new club in Europe
Pleasant viewing: Arsene Wenger watches his team cruise to victory from the sidelines
Passion: Napoli supporters stoked up a heated atmosphere at the Emirates Stadium
Pulling the strings: Aaron Ramsey was again influential for Arsenal in midfield
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